[12] 80번 12-086 김현수.fm

Journal of the Korean Ceramic Society

Vol. 49, No. 5, pp. 461~468, 2012.

461

http://dx.doi.org/10.4191/kcers.2012.49.5.461

The Photocatalytic Decompositions of 2-Chlorophenol on the Sn-impregnated Titania

Nanoparticles and Nanotube

Hyun Soo Kim, Gayoung Lee, Sun-Min Park*, and Misook Kang

Department of Chemistry, Yeungnam University, Gyeongsan 712-749, Korea

*Korean Institutes of Ceramic Engineering & Technology (KICET), Seoul 153-801, Korea

(Received August 17, 2012; Revised September 11, 2012; Accepted September 12, 2012)

Sn - 2-Chlorophenol

*

*

(2012 8 17 ; 2012 9 11 ; 2012 9 12 )

ABSTRACT

This study focuses on the difference of photocatalytic activity depending on crystal structure type of nanoparticles (TiO2) andnanotubes (TNT). The photodecomposition of 2-chlorophenol on the synthesized TiO2, Sn-impregnated TiO2, TNT, and Sn-impregnated TNT were evaluated. The characteristics of the synthesized photocatalyts, TNT, Sn/TNT, TiO2, and Sn/TiO2 wereanalyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-Visible spectroscopy (UV-Vis), and cyclicvoltammeter (CV). The water-suspended 2-chlorophenol photodegradation over TiO2 (anatase structure) catalyst was better than thatover pure TNT. Particularly, the water-suspended 2-chlorophenol of 10 ppm was perfectly decomposed within 4 h over Sn/TiO2photocatalyst.

Key words: Hydrothermal method, TiO2, Titania nanotube, Impregnation, 2-Chlorophenol photodegradation

1.

.

, ,

. 2-chlorophenol

, ,

.

.

,

.

,1,2) , ,

3,4)

.

.

.

2

.

(Advanced Oxidation Processes:

AOP). AOP pH UV

.

2

VOC .

OH

.5,8)

Corresponding author : Misook Kang

E-mail : [email protected]

Tel : +82-53-810-2363 Fax : +82-53-810-4613

462

.

,

OH

.

.

AOP

.

CO2 H2O

VOC .

TiO2 Si-TiO2 Pt-TiO2 ,

(

, )

.9-12)

.

(TiO2)

(Titania Nano Tube; TNT)

.

SnO2 Sn/TiO2 Sn/TNT

OH

.

X-ray (XRD),

(TEM), - (UV-

visible spectroscopy), BET (BET surface area),

(Cyclic voltammetry)

, 2-chlorophenol

, 2-

chlorophenol -

.

Fig. 1. Preparation of TiO2, TNT, Sn/TiO2, and Sn/TNT using a hydrothermal method.

Sn - 2-Chlorophenol 463

49 5(2012)

2.

TiO2 TNT

,13)

SnO2 Sn/TiO2 Sn/TNT

.14,15)

2.1. TiO2 TNT

TiO2 Fig. 1 250 mL

0.5 mol TTIP (titanium tetra iso-propoxide, Aldrich)

. 1 pH 3.0

.

200oC

5oC/min 8 .

pH 7.0 ,

80oC 24

TiO2 .

TNT 1 L 10 mol NaOH

1 .

TiO2

.

160oC 5

oC/min

10 .

pH 7.0

0.1 M HCl

, 80oC 24

TNT .

2.2. Sn/TiO2 Sn/TNT

100 mL TiO2 TNT

1 . 1.0 wt-% SnCl4

24 .

.

400oC 2

Sn/TiO2 Sn/TNT .

2.3.

TiO2, TNT, Sn/TiO2, Sn/TNT

X-ray (X-ray diffraction,

XRD, PANalytical , MPD) . Radiation

source CuK (=1.5056) , X-ray

generator 30 k, monochromator .

2=1080o 10

o/min

. (trans-

mission electron microscopy, TEM, HITACHI, S-

4100) , 200 kV .

pore size distribution BET-Japan

Inc. BELSORP-mini II BET

, pore size distribution

Kelvin meniscus

BJH (Barrett-Joyer-Hanlenda)

. 300oC 3 h

degassing . -

(UV-vis spectroscopy, SNINCO, Neosys-

2000) 2-chloro-

phenol .

2.4. 2-chlorophenol

Fig. 2

. 0.1 g

2-chlorophenol 10 ppm

. 365 nm UV-lamp (6 W/cm2, 3)

, 1 2-

chlorophenol UV-visible spectrometer

. 2-chlorophenol

2-chlorophenol .

2-chlorophenol 2-chlorophenol

(2 104

M) 250 mL . 2-chlorophenol

1, 3, 5, 7 9 mL

5 250 mL 8.0 107

,

2.4 106

, 4.0 106

, 5.6 106

M 2-chlorophenol

. 2-

chlorophenol 250 nm

.

3.

Fig. 3 TiO2, TNT, Sn/TiO2 Sn/TNT

Fig. 2. Apparatus of a photoreactor designed for 2-chlorophenol

degradation.

464

XRD . TNT

H2Ti3O7

11.3, 24.5, 29.78, 48.68 2 (d200), (d110),

(d003), (d020) .16)

Fig. 3(c) (d) TiO2 Sn/TiO2

(anatase)

25.3o, 37.79

o, 48.04

o, 55.1

o,

62.69o, 68.76

o, 75.1

o 2 (d101), (d004), (d200), (d105),

(d211), (d204), (d116) .17)

Fig. 3(b) Sn/TNT TiO2, TNT SnO2 (

; 29.86o, 33.29

o, 44.34

o, 57.38

o, 67.69

o18))

Sn TNT

TNT

.

Fig. 4 TiO2, TNT, Sn/TiO2 Sn/TNT

TEM . TNT 200~250 nm,

15~20 nm , Fig. 4(b)

Sn/TNT SnO2 TNT

. Fig. 4(c) TiO2

10~20 nm

. Sn Sn/TiO2

TiO2 SnO2

20~30 nm TiO2

.

Fig. 5 Table 1 /

BET

. N2 /

N2 BJH

. N2

01.0 BET

(SBET) .

IUPAC IV

TNT Sn Sn/TNT N2

Sn TNT

Fig. 3. XRD patterns of synthesized TiO2, Sn/TiO2, TNT, and

Sn/TNT photocatalysts.

Fig. 4. TEM images of synthesized (a) TNT, (b) Sn/TNT, (c) TiO2, and (d) Sn/TiO2 photocatalysts.


49 5(2012)

N2 . TNT,

Sn/TNT, TiO2 Sn/TiO2 73.26,

66.27, 135.40, 38.22 m2/g, TNT

TiO2 .

TNT single wall multi wall

. BJH

TNT, Sn/TNT, TiO2 Sn/TiO2

14.06, 16.85, 10.08 11.33 nm,

0.476, 0.161, 0.1847 0.1877 cm3/g.

Fig. 6 TNT, Sn/TNT, TiO2 Sn/TiO2

UV-Visible

. ,

.

.

Fig. 5. The isotherm curves for N2 adsorption/desorption on synthesized TiO2, Sn/TiO2, TNT, and Sn/TNT photocatalysts.

Table 1. BET Surface Area, Pore Volume, and Pore Diameter for Synthesized TiO2, Sn/TiO2, TNT, and Sn/TNT Photocatalysts

TNT Sn(1.0 wt-%)/TNT TiO2 Sn(1.0 wt-%)/TiO2

BET Mulipoint Surface area (m2g1

) 73.261 66.268 135.4 38.127

Total pore volume (cm3g1

) 0.476 0.161 0.1847 0.1877

Average pore diameter (nm) 14.061 16.854 10.084 11.327

Fig. 6. UV-Visible spectra for synthesized TiO2, Sn/TiO2,

TNT, and Sn/TNT photocatalysts.

466

,

,

. TNT

Sn

. TiO2 TNT

, Sn ( )

. Tauc TNT, Sn/

TNT, TiO2 Sn/TiO2

2.97, 3.01, 3.10 3.13eV.

Fig. 7 Ag/AgCl TNT, Sn/TNT,

TiO2 Sn/TiO2 .

. Sn Sn/TNT Sn/TiO2

.

redox

. Fig. 7 Sn

. TNT,

Sn/TNT, TiO2 Sn/TiO2

, (eV)/(eV) =

7.15/4.18, 6.94/3.93, 7.12/4.02 6.89/3.76

. TiO2 TNT Sn

,

( )

.

Fig. 8 TNT, Sn/TNT, TiO2 Sn/TiO2

(0.1 g) (Fig. 2) 10 ppm 2-

chlorophenol

. Fig. 8(a)-(c) 1

2-chloro-

phenol 1

2

. , TNT 14, Sn/TNT 9

Fig. 7. Cyclic voltammeter for synthesized (a) TNT, (b) Sn/TNT, (c) TiO2, and (d) Sn/TiO2 photocatalysts.

Fig. 8. Photodecomposition of 2-Chlorophenol using (a) TNT,

(b) Sn/TNT, (c) TiO2, and (d) Sn/TiO2.


49 5(2012)

, TiO2 5, Sn/TiO2, 4 10 ppm 2-

chlorophenol . TNT

TiO2

, TNT TiO2 Sn 1.0 wt-%

2-chlorophenol . Sn

redox( (

) ,

. Sn/

TiO2 Sn/TNT

5 .

TNT TiO2 2-chlorophenol

TiO2

. TiO2 2-chlorophenol

TNT

2-chlorophenol ,

TNT

.

4.

4 , TNT, Sn/TNT,

TiO2 Sn/TiO2

. XRD Sn/TNT

Sn TNT anatase

TiO2

TEM TNT TiO2

. UV-Visible

TNT < Sn/TNT < TiO2 < Sn/TiO2 Sn

. 2-chloro-

phenol , TNT 14, Sn/TNT 9

, TiO2 5, Sn/TiO2 4

. TNT TiO2 Sn

TNT Sn/TNT

TiO2 Sn/TiO2 2-chloro-

phenol .

Acknowledgment

(2011 )

.

REFERENCES

1. B. Guieysse, C. Hort, V. Platel, R. Munoz, M. Ondarts, and

S. Revah, Biological Treatment of Indoor Air for VOC

Removal: Potential and Challenges, Biotechnol. Adv., 26

398-410 (2008).

2. S. Santos, K. Jones, R. Abdul, J. Boswell, and J. Pacac,

Treatment of Wet Process Hardboard Plant VOC Emis-

sions by a Pilot Scale Biological System, Biochem. Eng. J.,

37 261-70 (2007).

3. S. H. Kwona and D. Cho, A Comparative, Kinetic Study on

Cork and Activated Carbon Biofilters for VOC Degrada-

tion, J. Ind. Eng. Chem., 15 129-35 (2009).

4. Y. C. Chiang, P. C. Chiang, and C. P. Huang, Effects of

Pore Structure and Temperature on VOC Adsorption on

Activated Carbon, Carbon, 39 523-34 (2001).

5. Y. H. Huang, Y. J. Huang, H. C. Tsai, and H. T. Chen, Deg-

radation of Phenol using Low Concentration of Ferric Ions

by the Photo-fenton Process, J. Taiwan. Inst. Chem. E., 41

699-704 (2010).

6. G. B. Ortiz de la Plata, O. M. Alfano, and A. E. Cassano,

Decomposition of 2-chlorophenol Employing Goethite as

Fenton Catalyst II: Reaction Kinetics of the Heterogeneous

Fenton and Photo-fenton Mechanisms, Appl. Catal. B-

Environ., 95 14-25 (2010).

7. J. M. Monteagudo, A. Duran, and C. Lopez-Almodovar,

Homogeneus Ferrioxalate-assisted Solar Photo-fenton

Degradation of Orange II Aqueous Solutions, Appl. Catal.

B-Environ., 83 46-55 (2008).

8. M. P. Moya, M. Graells, L. J. del Valle, E. Centelles, and H.

D. Mansilla, Fenton and Photo-fenton Degradation of 2-

Chlorophenol: Multivariate Analysis and Toxicity Moni-

toring, Catal. Today, 124 163-71 (2007).

9. Ch. Boughelouma and A. Messalhib, Photocatalytic Deg-

radation of Benzene Derivatives on TiO2 Catalyst, Physics.

Procedia., 2 1055-58 (2009).

10. Y. H. Chena, L. L. Chen, and N. C. Shang, Photocatalytic

Degradation of Dimethyl Phthalate in an Aqueous Solution

with Pt-doped TiO2-coated Magnetic PMMA Microspheres,

J. Hazard. Mater., 172 20-29 (2009).

11. M. A. Barakat, H. Schaeffera, G. Hayesa, and S. Ismat-Shah,

Photocatalytic Degradation of 2-Chlorophenol by Co-

doped TiO2 Nanoparticles, Appl. Catal. B-Environ., 57 23-

30 (2005).

12. D. N. Bui, S. Z. Kang, X. Li, and Jin Mu, Effect of Si Dop-

ing on the Photocatalytic Activity and Photoelectrochemical

Property of TiO2 Nanoparticles, Catal. Commun., 13 14-7

(2011).

13. I. C. Flores, J. N. de Freitas, C. Longo, M. A. de Paoli, H.

Winnischofer, and A. F. Nogueira, Dye-sensitized Solar

Cells Based on TiO2 Nanotubes and a Solid-state Elec-

trolyte, J. Photoch. Photobio. A., 189 153-60 (2007).

14. R. Vinu and G. Madras, Photocatalytic Activity of Ag-sub-

stituted and Impregnated Nano-TiO2, Appl. Catal. A - Gen.,

366 130-40 (2009).

15. R. Enderson, I. P. Diego, H.Z. dos S. Joo, B.C. P. Sibele,

468

and G. P. Fbio, Bentonites Impregnated with TiO2 for Pho-

todegradation of Methylene Blue, Appl. Clay. Sci., 48 602-

06 (2010).

16. K. P. Yu, W. Y. Yu, M. C. Kuo, Y. C. Liou, and S. H. Chien,

Pt/titania-nanotube: A Potential Catalyst for CO2 Adsorp-

tion and Hydrogenation, Appl. Catal. B-Environ., 84 112-

18 (2008).

17. B. S. Kwak, H. Choi, J. Woo, J. Lee, J. An, S. G. Ryu, and

Misook Kang, Photo-electrochemical Hydrogen Produc-

tion Over P- and B- Incorporated TiO2 Nanometer Sized

Photo-Catalysts, Clean Tech., 17 [1] 78-82 (2011).

18. S. Ken, O. Yuya, U. Hiroaki, H. Eiji, Z. Haoshen, and I.

Hiroaki, Aqueous Solution Synthesis of SnO Nanostrac-

tures with Tuned Optical Absorption and Photoelectro-

chemical Properties through Morphological Evolution, J.

Roy. Soc. Chem., 2 2424-30 (2010).

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[12] 80번 12-086 김현수.fm